Nickel double salts

Nickel is one of the metals that can form Tutton's salts. The singly charged ion can be any of the full range of potassium, rubidium, cesium, ammonium (), or thallium.[1] As a mineral the ammonium nickel salt, (NH4)2Ni(SO4)2 · 6 H2O, can be called nickelboussingaultite.[2] With sodium, the double sulfate is nickelblödite Na2Ni(SO4)2 · 4 H2O from the blödite family. Nickel can be substituted by other divalent metals of similar sized to make mixtures that crystallise in the same form.[3]

Nickel forms double salts with Tutton's salt structure with tetrafluoroberyllate with the range of cations of ammonia,[4] potassium, rubidium, cesium,[5] and thallium.[6]

Anhydrous salts of the formula M2Ni2(SO4)3, which can be termed metal nickel trisulfates, belong to the family of langbeinites. The known salts include (NH4)2Ni2(SO4)3, K2Ni2(SO4)3 and Rb2Ni2(SO4)3, and those of Tl and Cs are predicted to exist.

Some minerals are double salts, for example Nickelzippeite Ni2(UO2)6(SO4)3(OH)10 · 16H2O which is isomorphic to cobaltzippeite, magnesiozippeite and zinczippeite, part of the zippeite group.[7]

Double hydrides of nickel exist, such as Mg2NiH4.[8]

formula name mol struct cell Å ° V Z density colour refs
wt a b c β Å3 g/cm3
Li2[NiF(PO4)] Lithium nickel fluorophosphate 186.56 orthorhombic 10.473 6.289 10.846 714.3 8 3.469 [9]
Na2[NiF(PO4)] sodium nickel fluorophosphate 218.645 Pbcn 90 823.4 [10]
Na2Ni(SO4)2 · 4 H2O nickelblödite 368.867 monoclinic 11.045 8.193 5.535 100.50 2.487 green [11]
K2Ni2(SO4)3 potassium nickel trisulfate 483.77 orthorhombic 9.8436 9.8436 9.8436 90 3.369 [12]
Rb2Ni2(SO4)3 rubidium nickel trisulfate 576.51 9.9217 9.9217 9.9217 90 3.921 [13]
(NH4)2Ni2(SO4)3 ammonium nickel trisulfate 441.65 orthorhombic 9.904 9.904 9.904 90 3.02 [14]
(NH4)4Ni3(SO4)5 ammonium nickel pentasulfate 728.56 yellow [15]
NiLa(SeO3)2Cl nickel lanthanum diselenite chloride 486.977 hexagonal 8.666 18.662 1194.2 6 (153K) [16]
NiNd10(SeO3)12Cl8 nickel Neodymium diselenite chloride monoclinic 15.8175 1578,68 19.276 114.202 7407 4 (153K) [17]
Ni6Fe3+2(SO4)(OH)16 · 4 H2O honessite 904.08 trigonal 3.083 26.71 219.86 0.25 1.71 green [18]
NiTi(SO4)3 nickel titanium sulfate monoclinic 8.254 8.54 14.1444 124.967 817 4 3.21 [19]
Na2Ni(SeO4)2 · 2 H2O sodium nickel selenate dihydrate triclinic 5.507 5.905 7.172 α = 108.56 °, β = 99.07 °, γ = 106.35 ° 204.2 1 [20]
K2Ni(SeO4)2 · 2 H2O potassium nickel selenate dihydrate [21]
K2Ni(SeO4)2 · 6 H2O potassium nickel selenate Tuttons salt 527.52 monoclinic a b c 104.45 4 2.559 bright green [22]
Rb2Ni(SeO4)2 · 6 H2O rubidium nickel selenate Tuttons salt 619.62 monoclinic a b c 105.20 4 2.856 bright green [22]
Cs2Ni(SeO4)2 · 6 H2O caesium nickel selenate Tuttons salt 713.62 monoclinic 9.426 12.961 6.473 106.17 759.5 2 3.114 bright emerald green [22][23]
(NH4)2Ni(SeO4)2 · 6 H2O ammonium nickel selenate Tuttons salt 485.68 monoclinic a b c 106.29 4 2.243 bright green [22]
Tl2Ni(SeO4)2 · 6 H2O thallium nickel selenate Tuttons salt monoclinic a b c 105.60 4 3.993 bright green [24]
K2NiP2O7 310.85 monoclinic P21 9.230 17.540 8.32 91.44 1346.3 8 3.067 [25]
K6Sr2Ni5(P2O7)5 786.55 monoclinic P21/c 11.038 9.53 7.438 100.13 1578 2 3.309 yellow [25]
NaNi2(SO4)2[(H2O)(OH)] monoclinic C2/m Natrochalcite-type 8.605 6.185 7.336 114.78 354.5 2 [26]
BaNi2(PO4)2 barium nickel phosphate Trigonal R-3 4.8112 4.8112 23.302 467.1 3 green [27]
BaNi2(AsO4)2 barium nickel arsenate Trigonal R-3 4.945 4.945 23.61 532.59 3 5.31 [27]
BaNi2(VO4)2 barium nickel vanadate Trigonal R-3 5.0375 5.0375 22.33 3 [28]
Na4Ni7(AsO4)6 tetrasodium heptanickel hexaarsenate 1336.3 monoclinic C2/m 14.538 14.505 10.6120 118.299 1970.3 4 brown [29]
K2Ni(CO3)2 · H2O potassium nickel carbonate
Potassium tetraaquadicarbonatonickelate 		monoclinic Baylissite-type 6.755 6.156 12.2406 113.265 467.6 2 2.34 [30]
Rb2Ni(CO3)2 · H2O Rubidium nickel carbonate monoclinic Baylissite-type 6.971 6.348 12.2807 114.289 495.34 2 2.83 [31]
NiTh(NO3)6 · 8 H2O nickel thorium nitrate Monoclinic P21/c 9.089 8.728 13.565 96.65 1068.8(2) [32]
K[NiGa2(PO4)3(H2O)2] Potassium nickel(II) gallium phosphate hydrate 558.17 Monoclinic C2/c 13.209 10.173 8.813 107.68 1128.4 Z = 4 [33]
KNi3(PO4)P2O7 Potassium trinickel(II) orthophosphate diphosphate 484.14 Monoclinic 9.8591 9.3953 9.9778 118.965 808.63 4 [34]
KNiPO4 potassium nickel phosphate [35]
KNiPO4 · 6 H2O potassium nickel phosphate hexahydrate monoclinic P21 6.8309 11.0610 6.1165 91.045 462.07 2 [36]
NiK4(P3O9)2 · 7 H2O nickel potassium tricyclophosphate hydrate orthorhombic Fm2m 23.03 11.882 8.732 4 blue [37]
NiK4(P3O9)2 nickel potassium tricyclophosphate triclinic P-1 6.143 6.80 12.80 α=102.8 β=89.7 γ=66.03 473.56 1 [37]
NaK5Ni5(P2O7)4 Sodium pentapotassium pentanickel tetra(diphosphate) 1207.80 triclinic 7.188 9.282 10.026(5) α=109.31 β=90.02 γ=104.07 610.0 1 [38]
NH4NiPO4·H2O ammonium nickel phosphate hydrate orthorhombic 5.566 8.760 4.742 231.2 [39]
NH4NiPO4·6H2O ammonium nickel phosphate hydrate
Ni-struvite 		Orthorhombic Pmn21 6.924 6.104 11.166 471.5 2 [40][41][42]
LiNiPO4 lithium nickel phosphate orthorhombic 10.032 5.855 4.681 274.9 4 brown [43]
NaNiPO4 sodium nickel phosphate Pnma maricite structure 8.7839 6.7426 5.0368 298.31 4 yellow [44]
NaNiPO4 sodium nickel phosphate Pnma triphylite form 4.98 6.13 9.98 304.23 [45]
Na4Ni7(PO4)6 Cm 10.550 13.985 6.398 104.87 912.4 2 3.906 [44][46]
NaNiPO4 · 7 H2O sodium nickel phosphate heptahydrate tetrahedral P42/mmc 6.7390 10.9690 498.15 2 [36]
Na3NiP3O10 · 12 H2O trisodium nickel triphosphate dodecahydrate monoclinic (pseudoorthorhombic) 15.0236 9.1972 14.6654. 90.0492 2014.46 1.967 light green [47]
Na5Ni2(PO4)3 · H2O Pentasodium dinickel triphosphate hydrate monoclinic space group P21/n 14.0395 5.185 16.4739 110.419 [48]
Na6Ni2(PO4)3OH orthorhombic Pcmb 7.501 21.4661 7.173 [48]
Na2Ni3(OH)2(PO4)2 sodium nickel hydroxide phosphate monoclinic 14.259 5.695 4.933 104.28 2 3.816 [49]
NiNa4(P3O9)2 · 6 H2O nickel tetrasodium cyclotriphosphate hexahydrate triclinic 6.157 6.820 10.918 α=80.21 β=97.8 γ=119.5 409.8 1 [50]
NiRb4(P3O9)2 nickel tetrarubidium cyclotriphosphate P-31c 7.288 7.288 20.343 2 [51]
NiCs4(P3O9)2 · 6 H2O nickel tetracaesium cyclotriphosphate hydrate orthorhombic 19.992 6.500 18.445 4 [37]
NiCs4(PO3)6 nickel tetracaesium cyclotriphosphate rhombohedral P-31c 11.602 11.602 9.078 1058.24 2 [37]
NiAg4(P3O9)2 · 6 H2O nickel tetrasilver cyclotriphosphate hexahydrate triclinic 9.209 8.053 6.841 α=89.15 β=102.94 γ=97.24 1 [52]
NiAg4(P3O9)2 nickel tetrasilver cyclotriphosphate triclinic 6.100 6.783 10.764 α = 78.66 β=96.85 γ=113.36 401 1 [52]
Ni(NH4)4(P3O9)2 · 4 H2O nickel tetraammonium cyclotriphosphate tetrahydrate monoclinic 2 [53]
TlNi4(PO4)3 Thallium nickel triphosphate orthorhombic Cmc21 4 pale yellow [54]
Tl4Ni6(PO4)6 Thallium nickel hexaphosphate monoclinic Cm 4 yellow brown [54]
Tl2Ni4P2O7(PO4)2 monoclinic C2/c 8 brown [54]
NiMnSb Nickel manganese antimonide cubic 5.945 210.1 4 7.57 [55]
NiMnSi Nickel manganese silicide Orthorhombic 5.8967 3.6124 6.9162 147.32 4 [56][57]
NiMnGe orthorhombic Pnma 6.053 3.769 7.090 161.75 2 [58]
NiFeGe hexagonal [58]
TiNiSi orthorhombic [58]
NaNiIO6 sodium nickel periodate orthorhombic 8.599 2.492 10.281 220.3 [59]
KNiIO6 potassium nickel periodate orthorhombic 12.09 3.683 6.062 269.9 [59]
KNiIO6 potassium nickel periodate triclinic 6.4203 5.075 4.223 α= 65.07 β= 92.717 γ=109.95 116.51 [59]

Double fluorides include the above-mentioned fluoroanion salts, and those fluoronickelates such as NiF4 and NiF6. Other odd ones include an apple green coloured KNiF3·H2O and NaNiF3·H2O, aluminium nickel pentafluoride AlNiF5·7H2O, ceric nickelous decafluoride Ce2NiF10·7H2O, niobium nickel fluoride Ni3H4Nb2F20·19H2O, vanadium nickel pentafluoride VNiF5·7H2O, vanadyl nickel tetrafluoride VONiF4·7H2O, chromic nickelous pentafluoride CrNiF5·7H2O, molybdenum nickel dioxytetrafluoride NiMoO2F4·6H2O, tungsten nickel dioxytetrafluoride NiWO2F4·6H2O and NiWO2F4·10H2O, manganic nickel pentafluoride MnNiF4·7H2O, nickelous ferric fluoride FeNiF5·7H2O.[60]

Nickel trichloride double salts exist which are polymers. Nickel is in octahedral coordination, with double halogen bridges. Examples of this include RbNiCl3, pinkish tan coloured H2NN(CH3)3NiCl3.[61] Other double trichlorides include potassium nickel trichloride KNiCl3·5H2O,[62] yellow cesium nickel trichloride CsNiCl3,[62] lithium nickel trichloride LiNiCl3·3H2O,[62] hyrdrazinium nickel tetrachloride,[62] and nickel ammonium chloride hexahydrate NH4NiCl3·6H2O.[63]

The tetrachloronickelates contain a tetrahedral NiCl42− and are dark blue. Some salts of organic bases are ionic liquids at standard conditions.[64] tetramethylammonium nickel trichloride is pink and very insoluble.[65] Other tetrachlorides include rubidium nickel tetrachloride, lithium nickel tetrachloride Li2NiCl4·4H2O stable from 23 to 60°, stannous nickel tetrachloride , stannic nickel hexachloride is tetragonal.[66]

Lithium nickel hexachloride Li4NiCl6·10H2O is stable from 0 to 23°.

Copper nickel dioxychloride 2CuO·NiCl2·6H2O, and copper nickel trioxychloride 3CuO·NiCl2·4H2O.[62]

Cadmium dinickel hexachloride, crystallises in hexagonal system, dicadmium dinickel hexachloride, has rhombic crystals, and is pleochroic varying from light to dark green.[66]

Thallic nickel octochloride is bright green.[66]

Double bromides include the tetrabromonickelates, and also caesium nickel tribromide, CsNiBr3 copper nickel trioxybromide, 3CuO·NiBr2·4H2O mercuric nickel bromide, Hg2NiBr6, HgNiBr4. Aqueous nickel bromide reacting with mercuric oxide yields mercuric nickel oxybromide, didymium nickel bromide, is reddish brown (mixture of praseodymium and neodymium) Lanthanum nickel bromide, nickel stannic bromide (or nickel bromostannate) NiSnBr6·8H2O is apple green.[67][68]

The tetraiodonickelates are blood red coloured salts of the NiI4 ion with large cations. Double iodides known include mercuric nickel hexaiodide 2HgI2•NiI2 · 6 H2O, mercuric nickel tetraiodide HgI2•NiI2 · 6 H2O, and lead nickel hexaiodide I2•2NiI2 · 3 H2O.[69]

The diperiodatonickelates of nickel IV are strong oxidisers, and akali monoperiodatonickelates also are known.

Nickel forms double nitrates with the lighter rare earth elements. The solid crystals have the formula . The metals include La Ce Pr Nd Sm Gd and the non rare earth Bi. Nickel can also be replaced by similar divalent ions, Mg, Mn Co Zn. For the nickel salts melting temperatures range from 110.5° for La, 108.5° for Ce, 108° for Pr, 105.6° for Nd, 92.2° for Sm and down to 72.5° for Gd The Bi salt melting at 69°. Crystal structure is hexagonal with Z=3.[70] becomes ferromagnetic below 0.393 K.[71] These double nickel nitrates have been used to separate the rare earth elements by fractional crystallization.[72]

Nickel thorium nitrate has formula NiTh(NO3)6 · 8 H2O. Nickel atoms can be substituted by other ions with radius 0.69 to 0.83 Å. The nitrates are coordinated on the thorium atom and the water to the nickel. Enthalp of solution of the octahydrate is 7 kJ/mol. Enthalpy of formation is -4360 kJ/mol. At 109° the octahydrate becomes , and at 190° and anhydrous at 215°.[32] The hexahydrate has Pa3 cubic structure.[32]

Various double amides containing nickel clusters have been made using liquid ammonia as a solvent. Substances made include red Li3Ni4(NH2)11·NH3 (Pna21; Z = 4; a = 16.344(3) Å; b = 12.310(2) Å; c = 8.113(2) Å v=1631 D=1.942), and Cs2Ni(NH2)4•NH3 (P21/c; Z = 4; a =9.553(3) Å; b = 8.734(3) Å; c = 14.243(3) Å; β = 129.96(3)° V=910 D=2.960). These are called amidonickel compounds.[73] Yet others include Li4Ni4(NH2)12·NH3, Na2Ni(NH2)4,[74] orange red Na2Ni(NH2)4•2NH3,[75] Na2Ni(NH2)4•NH3, K2Ni(NH2)4•0.23KNH2, and Rb2Ni(NH2)4•0.23RbNH2.[73]

Nickel dihydrogen phosphide (Ni(PH2)2) can form orange, green or black double salts KNi(PH2)3) that crystallise from liquid ammonia. They are unstable above -78 °C, giving off ammonia, phosphine and hydrogen.[76]

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